Fuel compositions



United States Patent 3,025,148 FUEL COMPUSITIONS John D. Zach, Wilmington, Del., assignor to Atlas Chemical Industries, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed Aug. 29, 1958, Ser. No. 757,916 Claims. (Cl. 44-66) This invention relates to liquid hydrocarbon fuel compositions to which anti-static properties have been imparted and to methods of producing the same. Particularly it relates to liquid hydrocarbon fuels which have had their electrical characteristics changed by the addition of anti-static agents which are acylation products of certain polyhydroxy amino ethers.

Modern engines of the internal combustion type, such as are used in automotive vehicles and propeller driven aircraft, and jet engines, such as are used in military aircraft, make use of a wide variety of liquid hydrocarbon fuels. Many of these fuels have been found to present a serious safety hazard because of their property of forming an explosive equilibrium mixture with air at temperatures encountered under normal storage and handling conditions. Handling these fuels has, in the past, presented a considerable danger because such explosive mixtures may be readily ignited by discharges of static electricity which has been accumulated in the fuel in the course of pumping and transfer operations.

Not all fuels have volatility characteristics which ordinarily permit formation of explosive equilibrium mixtures at normal temperatures. Some fuels have such high volatility that they may not be expected to form such an explosive equilibrium mixture, except at temperatures below those normally encountered, because the vapor mixtures they form in equilibrium with air are too rich to be exploded. On the other hand, other fuels have such low volatility that, except under temperature conditions higher than those normally encountered, they may ordinarily not be expected to produce vapor mixtures which are rich enough to explode.

It should be appreciated that the above discussion is confined to equilibrium conditions. Fuels which do not normally form equilibrium explosive mixtures with air at normal temperatures may form explosive mixtures when compressed or when present with air in the form of a foam or froth. Thus, although automotive fuels do not form explosive equilibrium mixtures above 10 F., it is possible to obtain such mixtures in refinery operations at higher temperatures. For instance, when a tankful of automotive gasoline is blended by rolling with air (i.e. air is sparged into the tank as a source of agitation) an explosive mixture can be artificially created.

In general, the fuels with which the present invention will find its principal applicability are those having such volatility characteristics that, within a temperature range between about -20 F. and about 210 F., explosive equilibrium mixtures form in air and more particularly those which form such mixtures between about 20 F and about 100 F.

Reid vapor pressure, which is measured at 100 F., is one common measure of volatility characteristics.

Fuels suitable for use in this invention will be found 'ice is JP-3 jet fuel, which forms such mixtures at about 45 F. and below, and has a Reid vapor pressure between 5 and 7 pounds per square inch. The invention is also applicable to fuels which are used in internal combustion engines, as, for example, high test aviation gasoline which forms explosive mixtures at about 30 F. and below, and has a Reid vapor pressure between 5.5 and 7 pounds per square inch. It is also useful with kerosene and with ordinary automotive gasoline, which latter forms such explosive equilibrium mixtures at about 10 F. and below and has a Reid vapor pressure between 10 and 15 pounds per square inch. All of these fuels may be successfully treated in the manner described below and, when so treated, are within the scope of this invention.

When dealing with fuels, such as those discussed above, it has been found that an explosion can be triggered by the spark from a charge of static electricity such as can be built up in the fuel body in the course of pumping and filling operations. WADC Technical Report 55-266 of November 1954, entitled, Frictional Electrification Effects in Fuel Flow by Dr. F. M. Ernsberger of the Southwest Research Institute (catalogued by ASTIA as AD No. 90288) is a detailed study of the theoretical aspects of this problem. In order to minimize such dangers, many precautions are now taken such as elaborate grounding systems and the use of oversize pipe lines to minimize friction and consequent static build-up.

It has been empirically determined that there is a relationship between the electrical resistivity of liquid hydrocarbon fuels and their ability to build up a charge of static electricity such as is necessary to trigger an explosion. Fuels which have an electrical resistivity of less than about 1 x 10 ohm-centimeters cannot build up such a charge since the static charge created in such fuels is able, by virtue of the low resistivity thereof, to ground itself as fast as it builds up.

An object of this invention is, accordingly, the provision of liquid hydrocarbon fuel in which static electricity build-up during storage or handling is inhibited so as to minimize the possibility of accidental ignition.

An additional object of this invention is the provision of a fuel composition which is rendered highly conductive by the use of small amounts of selected additives, which additives do not interfere with the combustion characteristics of said fuel.

The above objects of this invention, as well as additional objects, will be apparent to those skilled in the art from a consideration of the following description and examples.

Briefly stated, it has been found that the fuels of the present invention have lower electrical resistivity (i.e. greater conductivity) and are inhibited against the buildup of static electricity by the addition of a small amount of anti-static agents which are acylation derivatives (i.e. amides and ester-amides) of polyhydroxy amino ethers formed by the seriatim reaction of a polyhydric alcohol, an epihalohydrin, and a basic nitrogen compound which contains at least two hydrogen atoms each of said hydrogen atoms being bonded to basic nitrogen.

The amount of additives of the invention desirable for anti-static protection is that which is sufiicient to reduce the electrical resistivity of the fuel to a value below about l l0 ohm-centimeters. Usually an amount less than 2 wt. percent will suffice and amounts between .0025% and 1.0% by weight are preferred.

The synthesis of the additives employed in this invention involves the following steps:

-(1) A polyhydric alcohol containing three of more hydroxyl groups per molecule, preferably a hexitol, is condensed with epichlorohydrin or a reactive compound similar to epichlorohydrin.

(2) The condensation product is in turn reacted with ammonia or an amine of the type described below.

(3) The product of step (2), which is in the form of a hydrohalide, is neutralized in a conventional manner with any suitable alkali to liberate a polyhydric amino ether.

(4) From these ethers, which are chemical intermediates, the acylation products (i.e. amides and ester amides) used in this invention as anti-static agents, as well as other reaction products can be derived. The anti-static agents of the invention can be synthesized by reacting the ethers with an aliphatic mono-carboxylic acid, in the manner described below.

The initial step of the synthesis is the condensation of a polyhydric alcohol having three or more hydroxyl groups per molecule with epichlorohydrin or its equivalent in the presence of a catalyst. The reaction can be exemplified by the following chemical equation:

[O-GHatJHOHrOlL.

R(OH): mCHzCHCHzCl R o ca (omm In the above equation x is a number of three or more and n is a number from one to x. R is an hydroxyl-free radical of a polyhydric alcohol. When the polyhydric alcohol is a hexitol, from one to about three mols of epichlorohydrin are usually preferred.

The reaction illustrated above may be performed in the presence of an acidic catalyst as is well known in the prior art. Preferred catalysts are those of the Lewis acid type which include, for example, BF BF etherate, AlCl SnCl but H 80 p-toluene sulfonic acid and the like may also be used.

The reaction may be carried out at any temperature from about 75 to 175 C., the preferred range being from 90 to 130 C. A temperature of 90 usually insures a reasonable reaction speed. Above about 130, decomposition and dehydration of hexitols often tends to occur.

While the reaction is generally carried out in the absence of solvent or diluent, such materials may be used if desired to lower the viscosity, as an aid in controlling temperature, or to permit the use of lower temperatures where high melting polyhydric alcohols (such as hexitols) are used.

Suitable polyhydric alcohols or mixtures thereof for use in this connection include, among others, triols (such as glycerol), tetritols (such as erythritol), pentitols (such as xylitol, arabitol, etc.), the hexitols (such as sorbitol, mannitol, dulcitol, etc.), polyhydric alcohols containing more than six hydroxy groups and polyhydric alcohols such as for example pentaerythritol, trimethylolethane, and trimethylolpropane which are polymethylol alkanes. Suitable polyhydric alcohols also include anhydro derivatives of other polyhydric alcohols (having at least three hydroxy groups per molecule) in which Water has been removed from two hydroxyl groups to form a cyclic ether, such as 1,4 sorbitan, and also external ethers of polyhydric alcohols, as, for example diglycerol.

Another group of suitable polyhydroxy alcohols comprises the monosaccharides such as sorbose, mannose, glucose, arabinose and xylose as well as methyl glucoside and similar compound.

The polyhydric alcohols useful in this invention include those, of the type listed above, which have been modified by etherification with alkylene oxides such as ethylene oxide, 1,2 propylene oxide and mixtures thereof. As is well known in the art, such a reaction yields products containing polyoxyalkylene chains of varying length. If a mixture of alkylene oxides is employed, a given polyoxyalkylene chain may contain both the oxyethylene group and the oxypropylene groups. For the purpose of utilization in this invention the most suitable polyoxyalkylene ethers of polyhydric alcohols are those formed by reacting from one to six mols of alkylene oxide with each mol of polyhydric alcohol. The term polyhydric alcohol when used herein is intended to include all of the above exemplified compounds and mixtures thereof.

In lieu of epichlorohydrin other reactive epihalohydrins may be used such as epibromohydrin and epiiodohydrin. Other compounds such as l-chloro-2,3 epoxybutane and 2-chloro-3,4 epoxybutane are also suitable for the condensation.

The reaction products are for the most part very viscous syrups. They are complex mixtures which may contain residual free polyhydric alcohol in addition to various isomeric epihalohydrin-polyhydric alcohol condensates (also referred to as chlorhydroxypropyl ethers).

The second step in the synthesis of suitable fuel additives involves the reaction of the condensation product of the initial step with ammonia, a reactive primary amine or a polyamine. The reaction with ammonia or a reactive primary amine may be illustrated by the equation set forth below.

(2) OH OH H01 toomoflomonn [OCHzJJHCHaI IHRIn R/ nRNH, R

(omx-n (oHh-n The reaction product, which is in the form of a hydrochloride, is neutralized in the next step with an alkali to liberate a polyhydric primary or secondary amino ether. This reaction may be illustrated as follows:

The symbols in the equation above have the same meaning as Equation 1. In addition, each R is independently selected from the group consisting of hydrogen, alkyl, hydroxy alkyl, cyclo alkyl, and polyhydroxy alkyl.

The reaction takes place between ammonia or a reactive primary aliphatic amine (primary amines having the amino group attached to tertiary carbon atoms, because of steric hindrance effects, will not react with the products of step (1) to give products which are suitable for the subsequent reaction and the term reactive amine, when used herein, is intended to exclude such amines) and the product of the first step synthesis. It is carried out in the presence of an excess of ammonia or reactive primary amine. The presence of the excess reactant serves to suppress polycondensation.

Preferred reaction temperatures range from 20 to about 120 C., with an optimum range from about 30 C. to about C. This reaction is exothermic and it may be carried out in an inert solvent, such as water or a lower alcohol. It is also possible to use an excess of the primary amine as a solvent where the primary amine being used is a liquid. In the case of ammonia or a volatile primary amine, such as methyl or ethyl amine, it is desirable to carry out the reaction under pressure so as to avoid the loss of the volatile reactant and thereby maintain it in excess of the theoretical molecular requirements.

By carrying out the reaction under super atmospheric pressure, higher temperatures can be used and the reaction time correspondingly reduced.

Suitable reactive primary mono-amines for use in this connection are exemplified by methyl amine, ethyl amine, n-propyl-amine, isopropyl amine, n-butyl amine, sec. butyl amine, isobutyl amine, n-amyl amine, n-hexyl amine, cyclo-hexyl amine, ethanol amine, propanol amine, and

1-amino-2,3 dihydroxy propane (glycerol amine) or mixtures thereof.

Mixtures of primary amines, such as hexadecyl, octadecyl, octadecenyl, and octadecadienyl may also be used. Such products are sold under the generic trademark Armeen. These products are more fully described on page 62 of the 1953 edition of Handbook of Material Trade Names by Zimmerman and Levine.

It is desirable, in many cases, to use the lower primary amines, which are sufliciently low-boiling, so that they can be readily separated by distillation from the reaction products which are non-volatile.

Suitable reactive amines also include polyamines which contain not more than 3 amino nitrogen atoms. Such amines are exemplified by the ethylene polyamines and the propylene polyamines and include ethylene diamine, diethylene triamine, propylene diamine, dipropylene triamine, triethylene triamine (N-aminoethyl piperazine), hydroxyethyl diethylene triamine (and other reaction products of lower alkylene oxides such as ethylene oxide, propylene oxide or mixtures thereof with polyamines, provided however, that the resulting oxyalkylated amine contains at least two amino hydrogens), 3,3 iminobis propylamine and mixtures of the above.

All of the above compounds (i.e. amines and ammonia) and wherein each B is independently selected fromthe group of monovalent radicals consisting of wherein further, in each radical, y is either 2 or 3; and each E is independently selected from the group consisting of hydrogen and hydroxy lower alkyl, provided however that at least one B is hydrogen.

The reaction with ammonia or primary amine produces a hydrochloride of an amino ether. The amino ether is liberated by the addition of an amount of alkali equivalent to the chlorine content of the epichlorohydrin condensate used. The excess ammonia or primary amine, as the case may be, is then stripped oif and can be recycled to the next batch.

The alkali used must be strong enough to liberate the amino ether from the amino hydrochloride and suitable alkalis are exemplified by the hydroxides of the alkali metals.

The amino ethers can be separated from the by-product alkali metal chloride by known methods, such as dilution with a non-solvent for the chloride followed by filtration and ion exchange. In some cases, the presence of the chloride is not objectionable and the product can be used without separating it.

Formation of the jet fuel additives is completed by amidation of the polyhydroxy amino ether with an aliphatic mono-carboxylic acid. Despite the selection of reaction conditions which favor the formation of amides, some esterification results. Since the amino ether contains free hydroxyl groups in the portion of the molecule derived from alcohol, and since further, it may contain additional free hydroxy groups if the primary amine used in the second step was an alkanol amine (such as, for instance, ethanol amine or propanol amine), there is always ester formation. Thus, the final reaction product is a combined amide and ester. The relative extent of amidation and esterification may be varied by varying the amount of fatty acid reacted with the polyhydroxy amino ether.

Amidation of the polyhydroxy amino ethers may be either total or partial. If only one amino nitrogen atom capable of amidation is present in the ether molecule, such as would be the case when the ether is formed by the seriatim reaction of one molecule of polyol, one molecule of epichlorohydrin and one molecule of a reactive primary monoamine, then the surface-active compositions of this invention are total amidation products. However, when more than one molecule of epichlorohydrin attaches to a given polyol molecule and/ or when a polyamine is used to form the amino ether then a molecule of the ether may contain a plurality of amino nitrogen atoms which are capable of amidation. In the case of such poly-amino ethers it is essential that at least one amino nitrogen be amidated. How many more will be amidated is a function of the carboxylzamino nitrogen ratio of reactants. While some e-sterification always occurs, lower ratios favor products which are predominantly amides whereas ratios above 1:1 tend to favor increased ester formation. Generally any ratio of carboxylztotal nitrogen from 0.75 to 6 may be used, those compounds prepared using ratios of from 3 to 6 having higher ester content. However, the range from 0.75 to 2.0 is generally preferred.

Total amidation of an ether derived from a primary mono-amine can be illustrated by the following equation:

x is a number of at least 3 and n is a number from 1 to x.

is the acyl radical of an aliphatic mono-carboxylic acid,

R is an hydroxyl-free radical of a polyhydric alcohol,

R is hydrogen, alkyl, cyclo alkyl, hydroxy alkyl or polyhydroxy alkyl,

Each R' is independently selected from the group consisting of hydrogen atoms and acyl radicals of aliphatic monocarboxylic acid, and

Each A is independently selected from the group consisting of hydrogen, alkyl, cyclo alkyl, hydroxy alkyl, polyhydroxy alkyl, acylated hydroxy alkyl, and acylated polyhydroxy alkyl,

In the case of the polyamines which have previously been described, the corresponding amidation products may be represented as having the formula:

wherein, further, y is an integer from 2 to 3, and each F is independently selected from the group consisting of hydrogen, acyl radicals of aliphatic monocarboxylic acids, hydroxy lower alkyl and acylated hydroxy lower alkyl, provided however that at least one F is the acyl radical of an aliphatic monocarboxylic acid.

The amidation reaction, in which at least one mol of H 0 is evolved per mol of acid reacted, is carried out at an elevated temperature, within the range of about 170 and about 220 C.

If none, or only part of the salt, was removed prior to this reaction, it can be filtered off from the amide either with or without dilution with a non-solvent for the salt. For some applications, the salt may be allowed to remain in the final product.

As has been stated, it is also possible to only partially amidate an amino ether which has been made from a polyolepihalohydrin derivative wherein the ratio of epihalohydrin to polyol Was greater than 1:1. Thus, the amidation products formed by reacting a monocarboxylic acid with the ether made from a polyol-epihalohydrin derivative and ammonia or a reactive primary monoamine may be generally represented by the following 70 formula:

wherein x is a number of at least 3; n is a number from 1 to x; and m is a number from zero to the quantity x-n; and wherein further,

The corresponding generalized formula for products formed from polyamine derivatives is as follows:

wherein B has the meaning assigned in Formula 3-A, D has the meaning assigned in Formula 4-A and x, m, n, R, and R have the same meaning as in Formula 5.

In the case where total amidation does not occur and consequently only part of the amino groups are reacted, the resulting amides will contain free amino groups and are, therefore cationic, whereas the fully amidated products are non-ionic.

Suitable mono-carboxylic acids for the amidation include the higher fatty acids such as lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, ricinoleic, l2-hydroxy stearic acid, erucic, as well as mixed acids such asthe fatty acids derived from animal and vegetable fats and oils, tall oil, naphthenic acids and acids obtained by the oxidation of petroleum fractions. While fatty acids having 12 to 18 carbon atoms are preferred for this reaction, it is also possible to use a short chain acid such as acetic acid, provided that the amino ether which is being amidated has a long alkyl chain which was derived from a fatty amine in the previous synthesis step.

As is well known in the art, emulsifiers have both a hydrophobe and a hydrophile function. In the present compounds, the hydrophobe function can be contributed by either the carbon chains derived from the amine or those derived from fatty acid, or both. Thus, when a short chain acid as, for example, acetic is employed, a long chain amine should be used. In general, it is preferred that the combined carbon chain lengths of amine and fatty acid groups used in the preparation of the additives of this invention total over 12.

The formation of suitable compounds is described more fully in my co-pending case, Serial No. 654,442, filed April 23, 1957, of which the instant case is a continuation-in-part. Such suitable compounds are particularly exemplified by Examples III-1 to III-33 in that case.

Anti-static additives suitable for use in this invention were synthesized in the following manner.

A. CONDENSATION OF A POLYHYDRIC ALCO- HOL WITH EPICHLOROHYDRIN Example A] 613 grams of anhydrous sorbitol were heated to a reaction temperature of between 97 and 107 C.; 1.5 cc. of BF (45% BF etherate catalyst were then added.

Thereafter, 389 grams (molal ratio 1:1.25) of epichlorohydrin were added dropwise over a period of 34 minutes with vigorous stirring and control of cooling, so as to maintain the temperature within the specified limit. The temperature was maintained for an hour thereafter between 97 and 107 C. by the addition of heat to insure completion of the reaction.

Example A-2 Following the procedure outlined in Example A-l, 1,200 grams of sorbitol were reacted with 1,220 grams of epichlorohydrin (molal ratio 1:2) using 3.0 cc. of the same catalyst. The epichlorohydrin was added over a period of minutes. Total reaction time was 2 hours and 20 minutes in the temperature range of 102 to 108 C.

Example A-3 Following the procedure of Example A-l, 729 grams of sorbitol were reacted with 925 grams of epichlorohydrin (molal ratio 122.5) using 2 cc. of the same catalyst. The epichlorohydrin was added over a period of r 9 70 minutes. Total reaction time was 2 hours and 10 minutes at a temperature range of from 98 to 108 C.

Example A-4 Following the procedure of Example A-l, 122 grams Example A-S Following the procedure of Example A-l, 1,184 grams of sorbitol were reacted with 602 grams of epichlorohydrin (molal ratio 1:1) using 3.0 cc. of the same cat alyst. The epichlorohydrin was added over a period of 38 minutes. Total reaction time was 1 hour and 38 minutes at temperatures ranging from 97 to 109 C.

B. REACTION OF ABOVE CONDENSATION PROD- UCT WITH AMMONIA OR AN AMINE Example B-1 467 grams of the condensation product of Example A-l were combined with 1,100 cc. of butyl amine at room temperature and the mixture was allowed to stand over night. The temperature gradually rose for several hours to about 35 to 40 C. and then gradually decreased. After standing over night, the reaction mixture was heated on a steam bath for several hours to insure completion of the reaction. Since butyl amine is a relatively volatile amine, some of the excess boiled olf during this heating.

The reaction mixture was then treated with an amount of aqueous NaOH equivalent to the chlorine contentof the epichlorohydrin condensate used. The excess amine and solvent were stripped ofi, using vacuum at the end of the stripping operation. Thereupon, the product was taken up in sufiicient methanol to obtain a suitable filtering viscosity and the crystalline NaCl was filtered off. The methanol was then stripped off, leaving the polyhydroxy amino ether as a residue.

Example B2 Following the procedure of Example Bl, 800 grams of the condensate of Example A-2 were reacted with 3,210 cc. of 40% methyl amine, yielding 782 grams of the amino ether after neutralization.

Example B3 Following the procedure of Example B-l, 734 grams of the condensate of Example A-2 were reacted with 2,000 cc. of ethanol amine. The yield of product after neutralization was 863 grams.

Example B-4 Following the procedure of Example Bl, 167 grams of the condensate of Example A-3 were reacted with 182 grams of glyce-ryl amine. The yield of product after neutralization was 249 grams.

Example BS Following the procedure of Example B-l, 500 grams of the condensate of Example A-3 were reacted with 1,930 cc. of 40% methyl amine. After neutralization, the yield of product was 488 grams.

Example B6 Following the procedure of Example 13-1, 413 grams of the product of Example A4 were reacted with 1,200

cc. of butyl amine. The yield of product after neutralization was 476.5 grams.

Example B 7 Following the procedure of Example B-l, 332 grams of the product of Example A-5 were reacted with 700 spam rs "1o cc. of ethylene diamine. The yield of product after neu tralization was 373 grams.

Example B8 Example B9 Following the procedure of Example Bl, 275 grams of the product of Example A-5 were reacted with grams of hydroxyethyl'ethylene diamine. The yield of product, after neutralization, was 357 grams.

C. ACYLATION OF AMINO-ETHERS WITH ALI- PHAT'IC MONO-CARBOXYLIC ACIDS Example C-l 218 grams of oleic acid were added to 250 grams of the product made in Example Bl (molal ratio carboxylzN, 1:1). The mixing took place between 70 and 100 C. Thereafter, the reactants were heated to the reaction temperature of between 178 and 205 C. and held there for a period of 3 hours and 50 minutes.

Initial viscosity was high, due to the formation of amine soaps. However, as the temperature was raised and the amidation proceeded, the viscosity decreased.

This composition is also the product of Example III5 of the parent case referred to above, and is more completely described therein.

Examplle C-2 Following the procedure of Example C-1, 212 grams of tallow fatty acids were reacted with 243 grams of the product of Example B-1 (molal ratio carboxylzN, 1:1). The reaction temperature was in the range of to 211 C. and the total reaction time was 3 hours and 50 minutes.

This composition is also the product of Example III-6 of the parent case.

Example C-3 Following the procedure of Example C-1, 268 grams of oleic acid were reacted with 202 grams of the ether of Example B2 (molal ratio 1:1). The total reaction time was 3 hours and the temperature range at which the reaction was conducted was 181 to 210 C. This composition is also the product of Example III-12 of the parent case.

Example C-4 In a similar manner, 192 grams of lauric acid were reacted with 204 grams of the ether product of Example B2 (molal ratio 1:1). The total reaction time was 2 hours and 50 minutes and the reaction temperatures were in the range of to 219 C. This composition is also the product of Example III-13 of the parent case.

Example C-5 In a similar manner, 254 grams of oleic acid were reacted with 201 grams of the ether product of Example B3 (molal ratio 1:1). The total reaction time was 2 hours and 15 minutes and the reaction temperatures range from 180 to 215 C. This composition is also the product of Example III-14 of the parent case.

Example C-6 In a similar manner, 274 grams of oleic acid were reacted with 223 grams of the ether prepared in Example B-4 (molal ratio 1:1). The reaction time was 2 hours and 30 minutes and the reaction temperatures were in the range of 185 to 219 C. This composition is also the product of Example III-9 of the parent case.

Example C-7 This product was prepared from 252 grams of lauric 11 acid and 249 grams of the ether prepared in Example B-5. The total reaction time was 2 hours and 30 minutes, the reaction temperatures ranged from 180 to 210 C. This product is also the product of Example III-11 of the parent case.

Example C-8 250 grams of stearic acid were reacted with 246 grams of the ether prepared in Example B-6 (molal ratio 1:1). Total reaction time was 2 hours and minutes and reaction temperatures ranged from 187 to 213 C. This composition is also described more fully as Example Ill-22 of the parent case.

Example C-9 234 grams of oleic acid were reacted with 179 grams of the ether prepared in Example B7 (molal ratio 0.75:1). Total reaction time was 2 hours and minutes and the reaction temperatures ranged from 176 to 208 C. This composition is also the product of Example III-29 of the parent case.

Example C-10 253 grams of oleic acid were reacted with 160 grams of the ether prepared in Example B-7 (molal ratio 0.9: 1). Total reaction time was 2 hours and 15 minutes and reaction temperatures ranged from 175 to 210 C. This composition is also the product of Example III-33 of the parent case.

Example C-1] 310 grams of oleic acid were reacted with 165 grams of the ether prepared in Example B-8 (molal ratio 0.75:1). Total reaction time was 3 hours and reaction temperatures ranged from 180 to 188 C. This composition is also the product of Example III-30 of the parent case.

Example C-12 370 grams of oleic acid were reacted with 165 grams of the product of Example B-8 (molal ratio 0.9:1). Total reaction time was 2 hours and 50 minutes and the reaction temperatures ranged from 175 to 211 C. This composition is also the product of Example III-32 of the parent case.

Example C-13 215 grams of oleic acid were reacted with 152 grams of the product of Example B-9 (molal ratio 0.911). Total reaction time was 2 hours and the reaction temperatures ranged from 177 to 213 C. This composition is also the product of Example III-31 of the parent case.

Additives of the above preparations were incorporated in fuel formulations which exemplified the invention. Typical formulations, in any of which each of the above additives, namely preparations C-l to C-13 inclusive, are suitable as anti-static agents are as follows:

FORMULATIONS 11*3 To successive portions of JP-4 jet fuel add .02 weight percent of each of the products of Examples C-l to C-13. Each of these fuel formulations (i.e. JP-4 jet fuel plus one specific additive) has a resistivity of less than about l 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 14-27 To successive portions of JP-4 jet fuel add .01 weight percent of each of the products of Examples C-l to C-13. Each of these fuel formulations (i.e. JP-4 jet fuel plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 28-40 To successive portions of JP-4 jet fuel add .005 weight percent of each of the products of Examples C-l to C-l3. Each of these fuel formulations (i.e. JP-4 jet fuel plus one specific additive) has a resistivity of less than about 12 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 4153 To successive portions of kerosene add 1.8 weight percent of each of the products of Examples C-l to 13. Each of these fuel formulations (i.e. kerosene plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATION S 54-06 To successive portions of non-leaded automotive gasoline add 0.5 weight percent of each of the products of Examples C-l to C-l3. Each of these fuel formulations (i.e. non-leaded automotive gasoline plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 67-7 9 To successive portions of aviation gasoline add 1.0 weight percent of each of the products of Examples C-l to C-13. Each of these fuel formulations (i.e. aviation gasoline plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS -92 To successive portions of JP-3 jet fuel add 0.05 weight percent of each of the products of Examples C-l to C-13. Each of these fuel formulations (i.e. JP-3 jet fuel plus one specific additive) has a resistivity of less than about 1X 10 ohm-centimeters and embodies the instant invention.

Formulations of the above type were tested to determine the eifect of the additives on the resistivity of JP-4 et fuel. The results of some of these tests are tabulated below:

Additive Weight Resistivity percent (ohm-cm.) additive None 4. 0X10" 0.025 1.2 10 Product of Example C-l 0.05 5.6?210" 8325 if? w Product of Example C-2 0.05 6.4%3 81325 1 Product of Example C-3 0.05 6.1?18 0.1 2. 8X10 8. 815 1. 9x10 2 6.4 10 Product of xample C-4 05 0x10, 3. (1)25 1. 4X10 .2 1 10 Product of Example (3-5 0. 05 5.7?18" 8525 i'i 1 1 Product of Example (3-6 0.05 4.3%18 8. (1)1 2. 9X10 l0 Product of Example (3-? 0.025 #2268 0.05 4.1)(10 8' )25 Lgxiga In Product of Example C-B 0. 05 Lg10 0.1 4.5Xl0 8-3;. duct fE 1 -7X10 PM o xampe O 9 x 05 31 x 00 0.1 1.7Xl0 0.01 2.4Xl0" 8.825 9.6X10 d E 1 5 6.0 10 Pro net of xampc C 10 0'1 32x10, 0.2 1.8X10 0.5 4.3Xl0 g. 8225 3. 0X10" 2. 1 Product of Example O-11 0.025 Lgglg l0 Product of Example (3-12 0. 05 8.325 7X10 10 Product of Example C-13 0. 05 4. gig 0.1 23x10 Rlcinoleic acid acylation product of sorbitoleplchlorohydrln (1:2) ethanolamlnc, product of 0.05 1.3 10 Example III-15 of parent case. 0.1 3. 3X10 Additive Weight Resistivity percent (ohm-cm.) additive Laurie amide of sorbitol-epichlorohydrin (1:2.5) 0.025 8. 6X10 methyl amine, product of Example III-11 of 0.05 4.1)(10 parent case. 0.1 1. 9X10 Laurie amide of sorbitol-epichlorohydrin (1:1) 0.025 1.8X10

cyclohexylamine. product of Example III-21 of 0.05 7v 3X10 parent case. 0.1 3.3)(10 The above formulations were also tested for ability to build up a charge of static electricity. When the treated fuels were continuously pumped through a closed loop, no static build-up was detected.

Having described my invention, what is claimed is: 1. A liquid hydrocarbon fuel having a resistivity of less than about 1X10" ohm-centimeters comprising a liquid hydrocarbon which forms an equilibrium explosive mixture with air between about -20 F. and about 100 F. and has a Reid vapor pressure of from about 0.1 to about 15' pounds per square inch and, as an anti-static additive, from 0.0025 to.2.0 weight percent of a composition prepared by (1) aminating the condensation product of a polyhydric alcohol, having from 3 to 6 hydroxyl groups per molecule, and an epihalohydrin with a basic nitrogencontaining compound selected from the group consisting of ammonia, reactive primary alkyl monoann'ne, reactive primary hydroxy lower alkyl monoamine, reactive primary cyclo alkyl monoamine, reactive primary polyhydroxy lower alkyl monoamine, and alkylene polyamines containing from 2 to 3 amino nitrogen atoms and at least 14 2 amino hydrogen atoms per molecule; (2) liberating polyhydroxy amine ether condensation products by neutralizing the product of step (1) with an alkali; (3) and thereafter acylating the polyhydroxy amino ether condensation products of step (2) to form a fatty acid amide.

2. The fuel of claim 1 in which the anti-static additive is prepared by acylating the polyhydroxy amino ether condensation products of step (2 with a fatty acid having from 12 to 18 carbon atoms per molecule.

3. The fuel of claim 2 in which the polyhydric alcohol is sorbitol and the epihalohydrin is epichlorohydrin.

4. The fuel of claim 3 in which the basic nitrogen-containing compound is ammonia.

5. The fuel of claim 3 in which the basic nitrogen-containing compound is methyl-amine.

6. The fuel of claim 3 in which the basic nitrogen-containing compound is ethylene diamine.

7. The fuel of claim 3 in which the basic nitrogen-containing compound is diethylene triamine.

8. The fuel of claim 2 in which the liquid hydrocarbon is a low vapor pressure, wide-cut, gasoline type hydrocarbon of the nature of JP-4 jet fuel and having a Reid vapor pressure of from 2 to 3 pounds per square inch, and the anti-static additive is present in amounts from 0.0025 to 1.0 weight percent.

9. The fuel of claim 8 in which the polyhydric alcohol is sorbitol and the epihalohydrin is epichlorohydrin.

10. The fuel of claim 9 in which the basic nitrogencontaining compound is ethylene diamine and the fatty acid acylating agent is oleic acid No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,025,148 March 13, 1962 John D. Zech It is certified that error appears in the above numbered patent requirin orrection and that the said Letters Patent should read as corrected below.

Column 14, line 2, for "amine" read amino Signed and sealed this 25th day of September 1962 (SEAL) Attest:

DAVID L. LADD ERNEST W. SWIDER Commissioner of Patents Attesting Officer 

1. A LOQUID HYDROCARBON FUEL HAVING A RESISTIVELY OF LESS THAN ABOUT 1X10'''' OHM-CENTIMETERS COMPRISING A LIQUID HYDROCARBON WHICH FORMS AN EQUILIBRIUM EXPLOSIVE MIXTURE WITH AIR BETWEEN ABOUT-20*F. AND ABOUT 100*F. AND HAS A REID VAPOR PRESSURE OF FROM ABOUT 0.1 TO ABOUT 15 POUNDS PER SQUARE INCH AND AS, ANTI-STATIC ADDITIVE FROM 0.00025 TO 2.0 WEIGHT PERCENT OF A COMPOSITION PREPARED BY (1) AMINATING THE CONDENSATION PRODUCT OF A POLYHYDRIC ALCHOL, HAVING FROM 3 TO6 HYDROXYL GROUPS PER MOLECULE, AND AN EPIHALOHYDRIN WITH A BASIC NITROGENCONTAINING COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMMONIA, REACTIVE PRIMARY ALKYL MONOAMINE, REACTIVE PRIMARY HYDROXY LOWER ALKYL MONOAMINE, REACTIVE PRIMARY CYCLO ALKYL MONOAMINE, REACTIVE PRIMARY POLYHYDROXY LOWER ALKYL MONOAMINE, AND ALKYLENE POLYAMINES CONTAINING FROM 2 TO 3 AMINO NITROGEN ATOMS AND AT LEAST 2 AMINO HYDROGEN ATOMS PER MOLECULE; (2) LIBERATING POLYHYDROXY AMINE ETHER CONDENSATION PRODUCTS BY NEUTRALIZING THE PRODUCT OF STEP(1) WITH AN ALKALI; (3) AND THEREAFTER ACYLATING THE POLYDROXY AMINO ETHER CONDENSATION PRODUCT OF STEP (2) TO FORM A FATTY ACID AMIDE. 